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Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis
58
Citations
53
References
2017
Year
Four new hybrid architectures containing a [Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]<sup>6-</sup> polyoxoanion, (en)[Cu<sub>3</sub>(ptz)<sub>4</sub>(H<sub>2</sub>O)<sub>4</sub>][Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]·24H<sub>2</sub>O (1), (Hbim)<sub>2</sub>[{Cu(bim)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>}<sub>2</sub>{Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>}]·5H<sub>2</sub>O (2), H<sub>2</sub>[Cu(dpdo)<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>][{Cu<sub>2</sub>(dpdo)<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>(CH<sub>3</sub>CN)}<sub>2</sub>{Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>}<sub>2</sub>]·9H<sub>2</sub>O (3), and (H<sub>2</sub>bpp)<sub>4</sub>[{Cu(H<sub>2</sub>O)<sub>2</sub>}{NaCo<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>}<sub>2</sub>]·10H<sub>2</sub>O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]<sup>6-</sup> as the guest. Compound 2 is constructed from [Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]<sup>6-</sup> polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]<sup>6-</sup> polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [Co<sub>2</sub>Mo<sub>10</sub>H<sub>4</sub>O<sub>38</sub>]<sup>6-</sup> polyoxoanions joined together by Na<sup>+</sup> and Cu<sup>2+</sup> cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.
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